Printing and dyeing of polyester and cellulosic fibers and blends thereof



United States Patent 3,494,716 PRINTING AND DYEING 0F POLYESTER ANDCELLULOSIC FIBERS AND BLENDS THEREOF William A. Hoffman, Wayne, N.J.,assignor to Alliance Color and Chemical Corporation, Newark, N.J., acorporation of New Jersey No Drawing. Filed Apr. 15, 1964, Ser. No.360.086

Int. (:1. D06p 3/82 US. or. s 21 13 Claims ABSTRACT OF THE DISCLOSUREColoring compositions for cellulosics and polyesters containing'azoiccompound and coupling component, a large proportion of urea, andsufiicient alkali to provide a pH between 12 and 14, together withoptional polyhydric alcohol; printing pastes comprising the foregoingcompositions and thickeners; and processes for coloring cellulosicand/or polyester fibers with the foregoing compositions.

The present invention relates to coloring procedures, and it will beparticularly described in connection with printing procedures.

The present invention will be especially described in its application tothe color printing of fabrics of cellulosic fibers and/0r polyesterfibers and it will be particularly described in its application to theprinting of textile fibers containing polyester fibers, such as Dacron,Kodel, Fortrel and Terylene, which may be combined with cellulosicfibers such as cotton, rayon and linen. Either type of fabric may beprinted according to this invention by itself or in various combinationsof polyester and cellulosic fibers.

It has been found that it does not give satisfactory results to printblends of polyester fibers and cellulosic fibers With printing pastes,particularly containing diazotiZed bases stabilized with organiccompounds such as methyl taurine or sarcosine together with couplingcomponents, since this requires a subsequent treatment or fixing ordeveloping operation with acid aging with fumes of acetic and/or formicacid to achieve hydrolysis of the stabilized base.

The need to acid age creates an obstacle to the use of azoic printingpastes by themselves or combined with other dyestuffs which cure or fixby other methods and it is difiicult to find a suitable way to couple ordevelop these azoic printing pastes under conditions which wouldsimultaneously induce development and fixation of other dyestuffs and itis a primary achievement of the present invention that printing orcoloring of textiles with azoic components may be achieved together withthe fixation and application of other dyestuffs thereto.

The acid aging process is not most effective with polyester fibers orcellulosic combinations containing polyester fibers, since uneveneffects are obtained and the cotton or cellulosic fiber is colored oraffected without any substantial effect upon the polyester fiber.

At the same time it has not been found satisfactory to print cotton orcotton-polyester combinations with insoluble disperse dyestuffs whichare not soluble in water and which require organic compounds ascarriers, such as benzoic acid, ortho phenyl phenol, methyl salicylate,diphenyl, or the sodium salts of these compounds or various other methylor ethyl, straight chain or cyclo, alkyl or hexyl phenols. Thedifficulty here is that the cotton will not be properly colored andthere will be considerable unevenness between the polyester fiber andthe cotton fiber.

It is a principal object of the present invention to provide a coloringprocedure, and preferably a color 3,494,716 Patented Feb. 10, 1970printing procedure, in which the color printing may be applied topolyester-cellulosic blends as well as polyester or cellulosic fibers bythemselves without changing the formulation for different percentages ofthese fibers and with the ability to print the separate fibersindividually, apart from the blends thereof.

A further object of the present invention is to provide an effectiveprinting composition or printing base which may be readily applied toeither cellulosic or cotton fibers on one hand or polyester fibers onthe other hand, or blends thereof, with assurance that color effectswill be achieved on the resultant fabrics, whether they be woven orknitted, without the necessity of acid fume aging.

Another object is to provide a printing system applicable to cellulosicfibers on one hand or polyester fibers on the other hand, or blendsthereof, which may be readily accomplished without multiple fixingtreatments and in which a simple, readily controlled printing processmay be achieved in commercially available equipment.

Still further objects and advantages will appear in the more detaileddescription set forth below, it being understood, however, that thismore detailed description is given by way of illustration andexplanation only and not by way of limitation, since various changestherein may be made by those skilled in the art without departing fromthe scope and spirit of the present invention.

It has been surprisingly found that printing pastes are most effectivefor application to cellulosic or polyester fibers or combinationsthereof, whether they contain azoic components alone or with disperse orother dyes, if there is developed after the printing operation atelevated temperature cyanic acid together with ammonia and ammoniumcarbonate.

These compounds are developed only after the print ing paste has beenapplied and the fabric has been dried, and the exposure and reactionshould take place during a period of less than 10 minutes and desirablybetween 20 seconds to 300 seconds.

The azoic components, with or without added disperse dyes, willeffectively react and develop colored insoluble organic pigments in andon the fibers above set forth when the exposure lasts between 15 secondsto about 350 seconds, and at a temperature of between 271 F. to about425 F. With the blended polyester cellulosic fibers, depending upon thepercentage of polyester and cellulosic fibers, the ranges may be from350 F. to 400 F. and for a period of 15 seconds to 300 seconds.

It has been found most important that the cyanic acid, together withcarbon dioxide be generated in situ. Desirably the reaction should haveaccess to air or with an exhaust so as to remove ammonia and ammoniacarbonate which are reaction byproducts which retard the rate ofreaction. The acid produced by the thermally induced reaction issufiicient to change the initial pH of the printed area from between 12to 14 down to between 7 to 7.5.

It has been found that the most effective method of achieving therelease of these compounds in situ is by the inclusion of a nitrogenousorganic compound in the printing composition in the amount of above 5%and desirably between 15 to and the most effective compound has beenfound to be urea, which has been first dissolved before application.

Urea has been found to be much more satisfactory than melamine,urethane, dicyandiamide, cyanuric acid, acetamide, or alkylated ormethylated derivatives thereof. These last mentioned compounds do notproduce an effective evolution of the cyanic acid nor of the carbondioxide to achieve the desired result. Tiourea may be utilized toreplace part or all of the urea.

It has been found that the urea in the print paste should be present inan amount varying from above to 35% and desirably from 15% to 30% in asolution containing a polyhydroxy or polyhydric alcohol, such asethylene glycol, glycerin, propylene glycol, sorbitol, mannitol andpentaerythritol.

In any case, however, in the final print composition it is necessarythat the urea never be less than 5% by Weight or desirably be not lessthan by weight. The glycerin or other polyhydric alcohol, when usedshould be present in not less than /2 to 3% by weight.

Desirably the urea in final print paste should not exceed 40% by weightand desirably should not exceed 30 to 35% by weight. The combination maybe printed from a composition containing a thickener, such as alginate,starch, modified starch or dextrin, or other thickeners.

The print paste, before application to the fabric, should have a pH ofbetween 8 and 14 and desirably a pH of 12 to 14, and this is mostdesirably achieved by adding an aqueous caustic alkali solution.Desirably, at a subsequent stage after drying and heating, the resultant developed, colored area should have a pH of between 7.0 and 8.5,and desirably of 7.0 to 7.5.

It is also possible to have present a small amount of alkyl ether of aglycol, such as mono, di or tri methyl, ethyl or propyl ether ofethylene or propylene glycol, which may be present in amount of 1 to 6%by weight and desirably about 4% by weight of the total combination,including the thickener and the water.

The glycol ether serves as a solvent and dispersing agent for thestabilized diazonium compound, the coupling component and the dispersedyestuflf, if present.

Where disperse dyes are also used, these may be present in relativelysmall amounts in the printing paste down to as low as and up to 10%.

The preferred diazo amino compounds are sodium or potassium sarcosidesor methyl taurides of the diazonium compounds of various a-mino aromaticcompounds, such as amino benzene, amino toluene, or substitutedaminobenzenes or amino-toluenes, including benzidine or substitutedbenzidines.

The preferred substituents are alkyl or alkoxy groups, halogens, nitrogroups, or substituted sulfonamides. These stabilized diazoniumcompounds are combined with .naphthalene compounds, such as hydroxynaphthoic acid condensed with aniline or toluidine or substitutedcompounds of the same character, such as methyl, ethyl, propyl, methoxyor ethoxy substituted compounds or other coupling compounds.

Desirably these coupling compounds are in approximately equimolarproportions with the diazo amino compounds and are present in amountranging from A to 5% by weight of the printing paste.

Where both the azoic components and the disperse dyes are present, thetotal is about 2 to 12% of both of these dyestuffs with about 1 to 6% ofthe azo dyestuff and 0.25 to 6% of the disperse dyestuif.

It is not preferred to use sodium cyanamide, S-sulfo 2-butyl amidobenzoic acid, diethanolamine and diisopropanolamine. The sarcosides andtaurides have been found to be most satisfactory.

Desirably a printing paste composed of a stabilized diazonium compoundand a coupling component in approximately equimolar ratio, a polyhydricalcohol, 10 to 35% urea, a glycol ether, sodium or potassium hydroxide,water and a suitable thickening agent, with or without a disperse dye isapplied to the fabric by any of several means, as for example withengraved rollers, machine screens, hand screens or block printing. Theprinted fabric may then be dried at normal operating temperaturesranging from 180 to 250 F.

Color development and fixation are obtained by subjecting the printed,dried fabric to dry heat without steaming in excess of 271 F for up to300 seconds. The optimum range on cotton is from 300-400 F. for 15 to 60seconds. The optimum range on a mixed fiber fabric such as a 65%Dacron/35% cotton shirting is from 350425 F. for 60 to 300 seconds.

Finally, the fabric is washed, and it has been found that there is amost satisfactory fixation and development of the color upon the cottonor other cellulosic and polyester fibers, single and combined, with thecolor being of uniform appearance and reproducible on a specific fabric.

EXAMPLE I Preferred Range Urea 25 15 to 35. Azoic components 1O 6 to 20.Monoethyl ether of ethylene glycol 4 1 to 6. Glycerin 2 to 4. Thickener59 50 to 70.

lecular weight 141.5 5.25 Naphthol ASD molecular Weight 277 4.575 NaOH50% solution 1.5 Monoethyl ether of ethylene glycol 10.0 Glycerin 5.0Urea 62.5 Water 11.175

In the above example, the first component is sodium sarcoside ofdiazonium compound of 5-chlor-2-amino toluene, and the second componentis the condensation product of o-toluidine with 2,3 oxynaphtholic acid.

EXAMPLE III Preferred parts Stabilized Red PT Sarcoside 41% aminemolecular weight 107 4.375 Naphthol ASD molecular weight 277 4.625 NaOH50% solution 1.5 Monoethyl ether of ethylene glycol 10.0 Glycerin 5.0Urea 62.5

Water 12.0

The first component is the sodium sarcoside of diazomum compound ofparatoluidine.

EXAMPLE IV Preferred parts l-amino 4-azobcnzene 7-naphthol 3.5 Anilideof 2,3 oxynaphthoic acid .5 Sodium methyl tauride of tetrazotizedo-dianisidin 4.0 NaOH 50% solution 1.5 Monoethyl ether of ethyleneglycol 10.0 Glycerin 5.0 Urea 45.0 Ester Scarlet 2GH a disperse dyeproduced by Harshaw Chemical Co, Ester Blue BLI-I a disperse dyeproduced by Harshaw Chemical Co. 7.5 Water 20.5

EXAMPLE V Preferred parts Naphthol ASG (4,4 bi orthoaceto-acetotoluidine) 2.200 NaOH 50% 1.100 Stabilized Red KB sarcoside53.4% amine molecular weight 141.5 3.075 Monoethyl ether of ethyleneglycol 10.000 Glycerin 5.000 Urea 62.500 Water 16.125

The first component is the condensation product of ethylacetoacetate ando-tolidine, the third component is the sodium sarcoside of the diazocompound of 4-chlor-2- amino toluene.

The above composition may be combined with a disperse dye bysubstituting for the 16.125 parts of water, 5.0 parts of Ester YellowYLH, a disperse dye produced by Harshaw Chemical Co. and 11.125 parts ofwater.

EXAMPLE VI Preferred parts Condensation product of 2-hydroxy-3-naphthoicEXAMPLE VII The preferred composition before addition of a thickener maybe prepared as follows:

Ingredient Preferred, parts Range, parts Nora-Normally the water shouldmake up the composition up to 100 parts by Weight.

In Examples I to VII all parts are by Weight. In Examples 11 to VIIthere are given compositions in parts by weight which may be preparedfor use with a suitable thickener in amounts ranging from 20 to 50 partsby Weight of the composition to 50 to 80 parts by weight of thethickener. Example I is an example of a printing paste ready for use.

The essential feature of the present invention is the inclusion ofsufiicient urea, ranging from above 5 to 35% by Weight of the thickenedprinting paste which, when applied to the fabric of cellulosic orpolyester fibers or blends thereof and subsequently dried andheat-treated at from 271 to 425 F. for 15 to 300 seconds, surprisinglyproduces the hydrolysis of a stabilized azo base and subsequent couplingthereof with coupling components, with fixation to the fiber to give asatisfactory degree of fastness and a uniform color, whether thepolyester be used by itself, the cellulosic fiber be used by itself, orwhether blends be used ranging from 0% of one to 100% of the other.

An important feature of the present invention resides in the fact thatthe printed material after drying is heated in a non-acidic dry or lowmoisture atmosphere, preferably with sufiicient air currents to carryoff any evolved gases.

The polyester fibers above referred to are usually condensation productsof ethylene glycol and terephthalic acid.

In connection with the azo components the first component desirablyincludes a readily hydrolyzable diazo amino aromatic compound which maybe substituted with alkyl, alkoxy, halogen, nitro, substitutedsulfonamide and amino groups.

The second azoic components are usually selected from the followinggroups:

(a) anilides of betaoxynaphthoic acid; (b) acetoacetarylides of aromaticamines; (c) carbazoles;

(d) pyrazolones.

The preferred stabilizers are sarcosine and methyltaurine.

Less preferably propyl glycine, methyl glucamine, 4-sulfanthranilicacid, N-substituted anthranilic acid, piperolic acid are used asstabilizers.

Although sodium and potassium hydroxide are the preferred alkalies,other alkaline materials such as alkaline salts may be employed to givea pH of above 8.

The present invention may be applied from an emulsion print paste of theoil in water or water in oil type. In this case the thickener is theemulsion.

Essentially the invention resides in a composition of azoic componentswith or without other coloring components and urea together with aglycol ether, polyhydric alcohol and an alkali for combination with athickener which will make a printing paste. Such paste will contain whenprepared an aromatic diazo amino compound with a coupling component suchas an anilid of beta oxynapththoic acid containing 5 to 35% of ureabased upon the final weight of the print preparation which may beapplied to a substrate such as cotton or polyester fibers or blendedcotton and polyester fibers, followed by drying and then heating in anon-acidic low moisture or dry atmosphere without steaming in excess of271 F. and usually from 3 seconds at 425 F. to about 45 seconds at 284F.

The times indicated are the elapsed times until color appears and doesnot include time required for more complete fixation.

In dyeing procedures the thickener may be eliminated.

By azoic components is included an azoic compound and a couplingcomponent. By polyhydroxy or polyhydric alcohol or compound is includedaliphatic alcohols having more than one hydroxy group. The coloringcomposition before addition to the thickener is desirably in the form ofa paste containing 10 to 25 of water and containing 35 to 75% of urea.By azoic coloring or printing compositions is included compoundscontaining such components.

The advantages of the present invention are not achieved where smallquantities of urea are employed in amounts less than 5% on the printingpaste as an antifreeze or as a solubilizing agent, as applied to azoiccomponents and disperse dyes. Moreover, urea is not efiective for thepurposes of the present invention at temperatures less than 271 F.

It has been clear that the inclusion of small amounts of urea is not atall effective with azoic compositions and combination thereof withdisperse dyes when developed and fixed by heat treatment only since onlypoor and non-commercial color values will be achieved and neitherdyestutr' would be properly fixed and during washing the majorproportion of the dyestuffs would be washed away.

Although the present invention particularly contemplates coloring orprinting blends of cellulosic and polyester fibers with azoiccompositions and disperse dyes without disadvantageously affectingeither coloring compounds or the color effect on the fibers, other dyesmay also be included such as acid dyes or direct cotton dyes.

As many changes could be made in the above printing and dyeing ofpolyester, cellulosic fibers and blends thereof, and many widelydifferent embodiments of this invention could be made without departurefrom the scope of the claims it is intended that all matter contained inthe above description shall be interpreted as illustrative and not in alimiting sense.

Having now particularly described and ascertained the nature of theinvention, and in what manner the same is to be performed, What isclaimed is:

1. A method of coloring cotton and polyester fibers singly and incombination which comprises applying to them a coloring compositioncontaining an azoic compound and a coupling component, a largeproportion of urea, alkali and a polyhydric alcohol said compositionhaving a pH between 12 and 14.

2. A method of coloring cellulosic and polyester fibers and blendsthereof which comprises applying thereto a urea-containing azoiccomposition having a pH of between 12 and 14 and then drying and heatingto above 270 F. Without steaming the fibers, said composition containingurea in large proportion.

3. The process of claim 2 wherein the composition contains a thickener.

4. A method of coloring cellulosic and polyester fibers and blendsthereof which comprises applying thereto azoic coloring compositioncontaining caustic alkali and polyhydric alcohol and having a pH ofbetween 12 and 14, said composition containing urea in large proportion,and then drying and heating to above 270 F. without steaming the fibers.

5. A coloring composition containing azoic compound and couplingcomponent, a large proportion of urea, and caustic alkali, saidcomposition having a pH between 12 and 14.

6. A coloring composition according to claim wherein the alkali issodium hydroxide or potassium hydroxide.

7. A coloring composition containing azoic compound and couplingcomponent, a large proportion of urea, polyhydric alcohol, and causticalkali, said composition having a pH between 12 and 14.

8. A composition according to claim 7 wherein the alkali is sodiumhydroxide or potassium hydroxide.

9. A coloring composition containing 35 to 80 parts of urea, 3 to 15parts of azoic components, 2 to 9 parts of polyhydroxy alcohol, and 5 to15 parts of an alkyl ether of a glycol and also /2 to 2 parts alkali, inparts by weight.

10. A printing paste comprising 25 parts of urea, 10 parts of azoiccomponents, 2 parts of polyhydric alcohol, 4 parts of an alkyl ether ofa glycol and to 60 parts of a thickener having a pH between 12 and 14.

11. A coloring composition containing an azoic compound and a couplingcomponent, a disperse dye, a glycol ether, a polyhydric alcohol, and analkali said composition having a pH between 12 and 14.

12. A printing composition containing 15 to 35 parts of urea, 5 to 20parts of azoic components, 1 to 6parts of a glycol ether, /2 to 4 partsof a polyhydric alcohol and to 70 parts of a thickener.

13. A printing composition containing 15 to 35 parts of urea, 5 to 20parts of azoic components, 1 to 6 parts of a glycol ether, /2 to 4 partsof a polyhydric alcohol and 50 to 70 parts of a thickener, and A to 10parts of a disperse dye.

References Cited UNITED STATES PATENTS 2,828,180 3/1958 Sertorio 8622,845,326 7/1958 Streck 846 3,266,863 8/1966 Price 821 X NORMAN G.TORCHIN, Primary Examiner T. J. HERBERT, 111., Assistant Examiner US.Cl. X.R.

